U.S. patent number 8,569,407 [Application Number 13/257,787] was granted by the patent office on 2013-10-29 for biodegradable material composed of a polymer comprising a porous metal-organic framework.
This patent grant is currently assigned to BASF SE. The grantee listed for this patent is Emi Leung, Ulrich Muller, Jan Kurt Walter Sandler, Gabriel Skupin, Antje Van der Net, Motonori Yamamoto. Invention is credited to Emi Leung, Ulrich Muller, Jan Kurt Walter Sandler, Gabriel Skupin, Antje Van der Net, Motonori Yamamoto.
United States Patent |
8,569,407 |
Leung , et al. |
October 29, 2013 |
**Please see images for:
( Certificate of Correction ) ** |
Biodegradable material composed of a polymer comprising a porous
metal-organic framework
Abstract
The present invention relates to a biodegradable material in the
form of a foil or a film, where the material comprises a polymer
comprising at least one porous metal-organic framework and the at
least one porous metal-organic framework comprises at least one at
least bidentate organic compound coordinated to at least one metal
ion. The invention further relates to food packaging comprising
such a material and also its use for the packaging of foods and the
use of a porous metal-organic framework for the absorption of
ethene in food packaging.
Inventors: |
Leung; Emi (Somerset, NJ),
Muller; Ulrich (Neustadt, DE), Sandler; Jan Kurt
Walter (Heidelberg, DE), Skupin; Gabriel (Speyer,
DE), Yamamoto; Motonori (Mannheim, DE), Van
der Net; Antje (Kassel, DE) |
Applicant: |
Name |
City |
State |
Country |
Type |
Leung; Emi
Muller; Ulrich
Sandler; Jan Kurt Walter
Skupin; Gabriel
Yamamoto; Motonori
Van der Net; Antje |
Somerset
Neustadt
Heidelberg
Speyer
Mannheim
Kassel |
NJ
N/A
N/A
N/A
N/A
N/A |
US
DE
DE
DE
DE
DE |
|
|
Assignee: |
BASF SE (Ludwigshafen,
DE)
|
Family
ID: |
42562411 |
Appl.
No.: |
13/257,787 |
Filed: |
March 17, 2010 |
PCT
Filed: |
March 17, 2010 |
PCT No.: |
PCT/EP2010/053467 |
371(c)(1),(2),(4) Date: |
September 20, 2011 |
PCT
Pub. No.: |
WO2010/106105 |
PCT
Pub. Date: |
September 23, 2010 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20120016066 A1 |
Jan 19, 2012 |
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Foreign Application Priority Data
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Mar 20, 2009 [EP] |
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09155687 |
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Current U.S.
Class: |
524/174;
524/301 |
Current CPC
Class: |
B65D
65/466 (20130101); C08J 5/12 (20130101); Y02W
90/10 (20150501); B65D 81/267 (20130101); C08J
2367/02 (20130101); Y02A 40/961 (20180101); Y02W
90/13 (20150501) |
Current International
Class: |
C08K
5/098 (20060101); B26D 7/27 (20060101); C08L
67/02 (20060101) |
Field of
Search: |
;524/174,301 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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19954404 |
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May 2001 |
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DE |
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10111230 |
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Sep 2002 |
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DE |
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10355087 |
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Jun 2005 |
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DE |
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102005053430 |
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May 2007 |
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DE |
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0790253 |
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Aug 1997 |
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EP |
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1106233 |
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Jun 2001 |
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EP |
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0792309 |
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Sep 2002 |
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EP |
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1525802 |
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Apr 2005 |
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EP |
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1702925 |
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Sep 2006 |
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EP |
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WO-92/09654 |
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Jun 1992 |
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WO |
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WO-96/15173 |
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May 1996 |
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WO |
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WO-96/15174 |
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May 1996 |
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WO |
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WO-96/15175 |
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May 1996 |
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WO |
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WO-96/15176 |
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May 1996 |
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WO |
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WO-96/21689 |
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Jul 1996 |
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WO |
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WO-96/21690 |
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Jul 1996 |
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WO |
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WO-96/21691 |
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Jul 1996 |
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WO |
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WO-96/21692 |
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Jul 1996 |
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WO |
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WO-96/25446 |
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Aug 1996 |
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WO |
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WO-96/25448 |
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Aug 1996 |
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WO |
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WO-98/12242 |
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Mar 1998 |
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WO |
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WO-2005/003622 |
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Jan 2005 |
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WO |
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WO-2005/017034 |
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Feb 2005 |
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WO |
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WO-2005/049892 |
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Jun 2005 |
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WO |
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WO-2006/074815 |
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Jul 2006 |
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WO |
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WO-2007/023134 |
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Mar 2007 |
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WO |
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WO-2007/054581 |
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May 2007 |
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WO |
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WO-2007/131955 |
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Nov 2007 |
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WO |
|
Other References
PCT IPRP in PCT/EP2010/053467, mailed Sep. 22, 2011, 6 pgs. cited
by applicant .
"Machine Translation of DE102005053430", May 16, 2007 , 13 pages.
cited by applicant .
"Machine Translation of DE19954404", May 17, 2001 , 15 pages. cited
by applicant .
"Machine Translation of EP1106233", Jun. 13, 2001 , 6 pages. cited
by applicant .
"Machine Translation of EP1525802", May 27, 2005 , 6 pages. cited
by applicant .
"Machine Translation of WO96/15176", May 23, 1996 , 16 pages. cited
by applicant .
"PCT International Search Report for PCT/EP2010/053467", Oct. 26,
2010, 2 pages. cited by applicant .
Chen, Banglin et al., "Interwoven Metal-Organic Framework on a
Periodic Minimal Surface with Extra-Large Pores", Science, vol. 291
Feb. 9, 2001, 4 pages. cited by applicant .
Eddaoudi, Mohamed et al., "Design and Synthesis of
Metal-Carboxylate Frameworks with Permanent Microporosity", Topics
in Catalysis 9 1999, pages 105-111. cited by applicant .
Li, Hallian et al., "Design and Synthesis of an Exceptionally
Stable and Highly Porous Metal-Organic Framework", Nature, vol. 402
Nov. 18, 1999, 6 pages. cited by applicant .
O'Keeffe, M. et al., "Section 1:Tutorial--Frameworks for Extended
Solids: Geometrical Design Principles", Journal of Solid State
Chemistry 152 2000, pp. 3-20. cited by applicant .
Sudik, Andrea C. et al., "Design, Synthesis, Structure, and Gas
(N2, Ar, CO2, CH4, and H2) Sorption Properties of Porous
Metal-Organic Tetrahedral and Heterocuboidal Polyhedra", Journal of
American Chemical Society 2005, pp. 7110-7118. cited by
applicant.
|
Primary Examiner: Uselding; John
Attorney, Agent or Firm: Servilla Whitney LLC
Claims
The invention claimed is:
1. A biodegradable material in the form of a foil or a film, where
the material comprises a polymer comprising at least one porous
metal-organic framework and the at least one porous metal-organic
framework comprises at least one at least bidentate organic
compound coordinated to at least one metal ion.
2. The material according to claim 1 which is present in the form
of a foil.
3. The material according to claim 2, wherein the foil has a
thickness of less than 100 .mu.m.
4. The material according to claim 1, wherein the polymer comprises
a polyester based on aliphatic and aromatic dicarboxylic acids and
aliphatic dihydroxy compounds.
5. The material according to claim 4, wherein the at least one
metal ion is comprises an ion selected from the group of metals
consisting of Mg, Ca and Al.
6. The material according to claim 1, wherein the at least one at
least bidentate organic compound comprises a compound derived from
formic acid, acetic acid or an aliphatic dicarboxylic or
polycarboxylic acid.
7. The material according to claim 1, wherein the at least one
metal-organic framework is present in a proportion of from 0.01% by
weight to 10% by weight based on the total weight of the
polymer.
8. A food packaging comprising a material according to claim 1.
9. A method of packaging a food comprising using packaging a food
in the presence of the material according to claim 1.
10. A method for the absorption of ethene in food packaging
comprising providing a porous metal-organic framework in food
packaging.
11. The material according to claim 1, wherein the polymer
comprises a polyester based on aliphatic and aromatic dicarboxylic
acids and aliphatic dihydroxy compounds; the at least one metal ion
comprises an ion selected from the group of metals consisting of
Mg, Ca and Al; and the at least one at least bidentate organic
compound comprises a compound derived from formic acid, acetic acid
or an aliphatic dicarboxylic or polycarboxylic acid.
12. The material according to claim 11, wherein the at least one
metal-organic framework is present in a proportion of from 0.01% by
weight to 10% by weight based on the total weight of the
polymer.
13. A food packaging comprising a material according to claim
11.
14. A food packaging comprising a material according to claim
12.
15. A method of packaging a food comprising packaging a food in the
presence of the material according to claim 11.
16. A method of packaging a food comprising packaging a food in the
presence of the material according to claim 12.
17. The method of claim 10, wherein the porous metal-organic
framework comprises: at least one metal ion selected from the group
of metals consisting of Mg, Ca and Al; and at least one at least
bidentate organic compound derived from formic acid, acetic acid or
an aliphatic dicarboxylic or polycarboxylic acid.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is the National Stage entry of PCT/EP2010/053467,
filed on Mar. 17, 2010, which claims priority to European Patent
application number 09155687.8, filed on Mar. 20, 2009, both of
which are incorporated herein by reference in their entireties.
FIELD
The present invention relates to a biodegradable material in the
form of a foil or a film, food packaging comprising such a material
and also its use.
BACKGROUND
It is known that ethene can accelerate the ripening of foods such
as fruit and vegetables. This is exploited by carrying out an
ethene treatment for the targeted ripening of, for example, fruit.
Equally, the emission of ethene by the fruit itself into the
environment during transport is disadvantageous.
Attempts are therefore made to remove the ethene liberated from the
surrounding gas again from foods such as fruit, if the food is
present in a closed compartment such as packaging. Various
absorbents have been proposed for this purpose in the literature.
Absorbents mentioned here are, for example, activated carbon,
zeolites or silica.
Thus, for example, EP-A 1 106 233 describes a process for the
adsorption of ethylene from gases over an organophilic zeolite as
absorbent for the storage and transport of easily perishable
fruits, plants and vegetables, where the storage and transport
takes place in virtually closed spaces.
Furthermore, EP-A 1 525 802 proposes inhibiting the ripening
process, in particular fruit, using a foil comprising a zeolite for
packaging.
In addition, in terms of environmental politics, such packaging
materials like foils have to meet the requirement that they are
easy to dispose of or to recycle. Owing to the high demands made of
packaging materials for food such as fruit and vegetables from a
food technology point of view, biodegradable materials are
particularly preferred. Packaging materials such as foils composed
of biodegradable polymers are likewise known in the prior art.
Thus, for example, WO-A 2005/017034 and WO-A 2006/074815 describe
such biodegradable polyester mixtures.
Despite the materials known in the prior art for use in conjunction
with food, there continues to be a need for alternative
materials.
SUMMARY
According to one or more embodiments, provided is a biodegradable
material in the form of a foil or a film, where the material
comprises a polymer comprising at least one porous metal-organic
framework and the at least one porous metal-organic framework
comprises at least one at least bidentate organic compound
coordinated to at least one metal ion. Certain embodiments relate
to food packaging comprising such a material and also its use for
the packaging of foods, as well as the use of a porous
metal-organic framework for the absorption of ethene in food
packaging.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 shows the ethene absorption at 298 K of a framework in
accordance with one or more embodiments of the invention.
DETAILED DESCRIPTION
It is therefore an object of the present invention to provide such
alternative materials which firstly inhibit the undesirable
ripening process during storage or transport of foods and also
satisfy the requirements for environmental compatibility of the
packaging used for the foods.
The object is achieved by a biodegradable material in the form of a
foil or a film, where the material comprises a polymer comprising
at least one porous metal-organic framework and the at least one
porous metal-organic framework comprises at least one at least
bidentate organic compound coordinated to at least one metal
ion.
It has been found that biodegradable polymers which are known per
se can particularly advantageously comprise porous metal-organic
frameworks as additive in said polymer for the absorption of
ethylene, and the desired absorption can occur in this way.
Biodegradable materials in the form of a foil or a film comprising
a polymer are known in the prior art. Their use as packaging
material has also been described.
Here, for example, foils having a thickness of preferably less than
100 .mu.m can be used. The thickness of a film can also be matched
to the respective use. However, the biodegradable material is
preferably a foil. The foil or film more preferably has a thickness
of less than 50 .mu.m, in particular of less than 25 .mu.m.
For the purposes of the present invention, a polymeric material is
biodegradable when it is completely biodegradable in accordance
with DIN EN 13432, part 2, which is the case when at least 90% of
the organic carbon of the material has been converted during a test
time of not more than 180 days.
The polymer is preferably a polyester based on aliphatic and
aromatic dicarboxylic acids and aliphatic dihydroxy compounds. Such
materials are marketed, inter alia, under the trade name
Ecoflex.RTM. by BASF SE.
Examples of polymers are described in the form of mixtures in WO-A
2005/017034 and WO-A 2006/074815.
Accordingly, the preferred polyesters based on aliphatic and
aromatic dicarboxylic acids and aliphatic dihydroxy compounds can
be present as such or as component i as described below.
Biodegradable mixtures of i) synthetic polyester materials and ii)
homopolyesters or copolyesters selected from the group consisting
of polylactide, polycaprolactone, polyhydroxyalkanoates and
polyesters derived from aliphatic dicarboxylic acids and aliphatic
diols are known (see EP-B 792 309). Such mixtures ideally combine
the desirable properties of the individual components, for example
the generally good processing and mechanical properties of
synthetic polyesters with the usually cheaper availability and
ecologically acceptable preparation and disposal of the polymers
listed above under ii), e.g. polylactide, polycaprolactone,
polyhydroxyalkanoates and polyesters derived from aliphatic
dicarboxylic acids and aliphatic diols.
The above-described polyesters i) and ii) can be used separately or
as a mixture. The same applies to the component iii) which is
described in more detail below. Preference is given to the polymers
i) and mixtures with these. Mixtures of the polymers i), ii) and
iii) are preferentially discussed below, but the same also applies,
for the purposes of the present invention, when only one polymer,
for example polymer i), is present as part of the biodegradable
material.
Possible components i for the production of the biodegradable
polyester mixtures are in principle all polyesters based on
aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy
compounds, known as partially aromatic polyesters. Mixtures of a
plurality of such polyesters are of course also suitable as
component i.
For the purposes of the invention, partially aromatic polyesters
also encompass polyester derivatives such as polyether esters,
polyesteramides or polyether esteramides. Suitable partially
aromatic polyesters include linear polyesters which have not been
chain extended (WO 92/09654). Preference is given to chain-extended
and/or branched partially aromatic polyesters. The latter are known
from the documents mentioned above, WO 96/15173 to 15176, 21689 to
21692, 25446, 25448 or WO 98/12242, which are hereby expressly
incorporated by reference. Mixtures of different partially aromatic
polyesters are likewise possible. Among partially aromatic
polyesters, particular mention may be made of products such as
Ecoflex.RTM. (BASF Aktiengesellschaft) and Eastar.RTM. Bio
(Novamont).
Particularly preferred partially aromatic polyesters include
polyesters comprising, as significant components, A) an acid
component comprising a1) from 30 to 99 mol % of at least one
aliphatic dicarboxylic acid or at least one cycloaliphatic
dicarboxylic acid or ester-forming derivatives thereof or mixtures
thereof, a2) from 1 to 70 mol % of at least one aromatic
dicarboxylic acid or ester-forming derivative thereof or mixtures
thereof and a3) from 0 to 5 mol % of a compound comprising
sulfonate groups, B) a diol component selected from among at least
one C.sub.2-C.sub.12-alkanediol and at least one
C.sub.5-C.sub.10-cycloalkanediol and mixtures thereof and also, if
desired, one or more components selected from among C) a component
selected from among c1) at least one dihydroxy compound comprising
ether functions and having the formula I
HO--[(CH.sub.2).sub.n--O].sub.m--H (I) where n is 2, 3 or 4 and m
is an integer from 2 to 250, c2) at least one hydroxy carboxylic
acid of the formula IIa or IIb
##STR00001## where p is an integer from 1 to 1500 and r is an
integer from 1 to 4 and G is a radical selected from the group
consisting of phenylene, --(CH.sub.2).sub.q--, where q is an
integer from 1 to 5, --C(R)H-- and --C(R)HCH.sub.2, where R is
methyl or ethyl, c3) at least one amino-C.sub.2-C.sub.12-alkanol or
at least one amino-C.sub.5-C.sub.10-cycloalkanol or mixtures
thereof, c4) at least one diamino-C.sub.1-C.sub.8-alkane, c5) at
least one 2,2'-bisoxazoline of the general formula III
##STR00002## where R.sup.1 is a single bond, a (CH.sub.2).sub.z
alkylene group, where z=2, 3 or 4, or a phenylene group, c6) at
least one aminocarboxylic acid selected from the group consisting
of natural amino acids, polyamides obtainable by polycondensation
of a dicarboxylic acid having from 4 to 6 carbon atoms and a
diamine having from 4 to 10 carbon atoms, compounds of the formulae
IVa and IVb
##STR00003## where s is an integer from 1 to 1500 and t is an
integer from 1 to 4 and T is a radical selected from the group
consisting of phenylene, --(CH.sub.2).sub.u--, where u is an
integer from 1 to 12, --C(R.sup.2)H-- and --C(R.sup.2)HCH.sub.2,
where R.sup.2 is methyl or ethyl, and polyoxazolines having the
repeated unit V
##STR00004## where R.sup.3 is hydrogen, C.sub.1-C.sub.6-alkyl,
C.sub.5-C.sub.8-cycloalkyl, unsubstituted phenyl or phenyl
substituted by up to three C.sub.1-C.sub.4-alkyl groups or is
tetrahydrofuryl, or mixtures of c1 to c6 and D) a component
selected from among d1) at least one compound having at least three
groups capable of ester formation, d2) at least one isocyanate, d3)
at least one divinyl ether and mixtures of d1) to d3).
The acid component A of the partially aromatic polyesters
comprises, in a preferred embodiment, from 30 to 70 mol %, in
particular from 40 to 60 mol %, of a1 and from 30 to 70 mol %, in
particular from 40 to 60 mol %, of a2.
As aliphatic acids and the corresponding derivatives a1, it is
generally possible to use those having from 2 to 10 carbon atoms,
preferably from 4 to 6 carbon atoms. They can be either linear or
branched. The cycloaliphatic dicarboxylic acids which can be used
for the purposes of the present invention are generally those
having from 7 to 10 carbon atoms and in particular those having 8
carbon atoms. However, it is in principle also possible to use
dicarboxylic acids having a larger number of carbon atoms, for
example up to 30 carbon atoms.
Mention may be made by way of example of: malonic acid, succinic
acid, glutaric acid, 2-methylgiutaric acid, 3-methyglutaric acid,
adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric
acid, 2,2-dimethylglutaric acid, suberic acid,
1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic
acid, 1,3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic
acid, maleic acid and 2,5-norbornanedicarboxylic acid.
As ester-forming derivatives of the abovementioned aliphatic or
cycloaliphatic dicarboxylic acids which can likewise be used,
particular mention may be made of the di-C.sub.1-C.sub.6-alkyl
esters, e.g. dimethyl, diethyl, di-n-propyl, diisopropyl,
di-n-butyl, diisobutyl, di-t-butyl, di-n-pentyl, diisopentyl or
di-n-hexyl esters. Anhydrides of the dicarboxylic acids can
likewise be used.
The dicarboxylic acids or their ester-forming derivatives can here
be used either individually or as a mixture of two or more
thereof.
Preference is given to using succinic acid, adipic acid, azelaic
acid, sebacic acid, brassylic acid or their respective
ester-forming derivatives or mixtures thereof. Particular
preference is given to using succinic acid, adipic acid or sebacic
acid or their respective ester-forming derivatives or mixtures
thereof. Particular preference is given to using adipic acid or its
ester-forming derivatives, e.g. its alkyl esters, or mixtures
thereof. Sebacic acid or mixtures of sebacic acid with adipic acid
are preferably used as aliphatic dicarboxylic acid when polymer
mixtures having "hard" or "brittle" components ii), for example
polyhydroxybutyrate or in particular polylactide are produced.
Succinic acid or mixtures of succinic acid with adipic acid are
preferably used as aliphatic dicarboxylic acid when polymer
mixtures having "soft" or "tough" components ii), for example
polyhydroxybutyrate-co-valerate, are produced.
In addition, succinic acid, azelaic acid, sebacic acid and
brassylic acid have the advantage that they can be obtained as
renewable raw materials.
Possible aromatic dicarboxylic acids a2 are in general those having
from 8 to 12 carbon atoms and preferably those having 8 carbon
atoms. Mention may be made by way of example of terephthalic acid,
isophthalic acid, 2,6-naphthoic acid and 1,5-naphthoic acid and
also ester-forming derivatives thereof. Particular mention may here
be made of the di-C.sub.1-C.sub.6-alkyl esters, e.g. dimethyl,
diethyl, di-n-propyl, diisopropyl, di-n-butyl, diisobutyl,
di-t-butyl, di-n-pentyl, diisopentyl or di-n-hexyl esters. The
anhydrides of the dicarboxylic acids a2 are likewise suitable
ester-forming derivatives.
However, aromatic dicarboxylic acids a2 having a larger number of
carbon atoms, for example up to 20 carbon atoms, can in principle
also be used.
The aromatic dicarboxylic acids or their ester-forming derivatives
a2 can be used either individually or as a mixture of two or more
thereof. Particular preference is given to using terephthalic acid
or its ester-forming derivatives such as dimethyl
terephthalate.
As compound comprising sulfonate groups, use is usually made of an
alkali metal or alkaline earth metal salt of a dicarboxylic acid
comprising sulfonate groups or ester-forming derivatives thereof,
preferably alkali metal salts of 5-sulfoisophthalic acid or
mixtures thereof, particularly preferably the sodium salt.
In a preferred embodiment, the acid component A comprises from 40
to 60 mol % of a1, from 40 to 60 mol % of a2 and from 0 to 2 mol %
of a3. In a further preferred embodiment, the acid component A
comprises from 40 to 59.9 mol % of a1, from 40 to 59.9 mol % of a2
and from 0.1 to 1 mol % of a3, in particular from 40 to 59.8 mol %
of a1, from 40 to 59.8 mol % of a2 and from 0.2 to 0.5 mol % of
a3.
In general, the diols B are selected from among branched or linear
alkanediols having from 2 to 12 carbon atoms, preferably from 4 to
6 carbon atoms, and cycloalkanediols having from 5 to 10 carbon
atoms.
Examples of suitable alkanediols are ethylene glycol,
1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol,
1,5-pentanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol,
2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol,
2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl-1,6-hexanediol,
in particular ethylene glycol, 1,3-propanediol, 1,4-butanediol and
2,2-dimethyl-1,3-propanediol (neopentyl glycol); cyclopentanediol,
1,4-cyclohexanediol, 1,2-cyclohexanedimethanol,
1,3-cyclohexane-dimethanol, 1,4-cyclohexanedimethanol or
2,2,4,4-tetramethyl-1,3-cyclobutanediol. Particular preference is
given to 1,4-butanediol, in particular in combination with adipic
acid as component a1), and 1,3-propanediol, in particular in
combination with sebacic acid as component a1). 1,3-Propanediol has
the additional advantage that it is available as renewable raw
material. It is also possible to use mixtures of various
alkanediols.
Depending on whether an excess of acid or OH end groups is desired,
either the component A or the component B can be used in excess. In
a preferred embodiment, the molar ratio of the components A:B used
can be in the range from 0.4:1 to 1.5:1, preferably in the range
from 0.6:1 to 1.1:1.
Apart from the components A and B, the polyesters on which the
polyester mixtures according to the invention are based can
comprise further components.
As dihydroxy compounds c1, preference is given to using diethylene
glycol, triethylene glycol, polyethylene glycol, polypropylene
glycol and polytetrahydrofuran (polyTHF), particularly preferably
diethylene glycol, triethylene glycol and polyethylene glycol, with
it also being possible to use mixtures thereof or compounds which
have different variables n (see formula I), for example
polyethylene glycol comprising propylene units (n=3), which can be
obtained, for example, by polymerization by methods know per se of
firstly ethylene oxide and subsequently using propylene oxide,
particularly preferably a polymer based on polyethylene glycol
having different variables n, where units formed from ethylene
oxide predominate. The molecular weight (M.sub.n) of the
polyethylene glycol is generally selected in the range from 250 to
8000 g/mol, preferably from 600 to 3000 g/mol.
In one of the preferred embodiments, it is possible to use, for
example, from 15 to 98 mol %, preferably from 60 to 99.5 mol %, of
diols B and from 0.2 to 85 mol %, preferably from 0.5 to 30 mol %,
of dihydroxy compounds c1, based on the molar amount of B and c1,
for preparing the partially aromatic polyesters.
In a preferred embodiment, the hydroxycarboxylic acid c2) used is:
glycolic acid, D-, L-, D,L-lactic acid, 6-hydroxyhexanoic acid,
cyclic derivatives thereof, e.g. glycolide (1,4-dioxane-2,5-dione),
D-, L-dilactide (3,6-dimethyl-1,4-dioxane-2,5-dione),
p-hydroxybenzoic acid and oligomers and polymers thereof, e.g.
3-polyhydroxybutyric acid, polyhydroxyvaleric acid, polylactide
(obtainable, for example, as EcoPLA.RTM. 2000D (from Cargill)) or a
mixture of 3-polyhydroxybutyric acid and polyhydroxyvaleric acid
(the latter is obtainable under the name Biopol.RTM. from Zeneca);
the low molecular weight and cyclic derivatives thereof are
particularly preferred for the preparation of partially aromatic
polyesters.
The hydroxycarboxylic acids can be used, for example, in amounts of
from 0.01 to 50% by weight, preferably from 0.1 to 40% by weight,
based on the amount of A and B.
As amino-C.sub.2-C.sub.12-alkanol or
amino-C.sub.6-C.sub.10-cycloalkanol (component c3), which for the
present purposes also includes 4-aminomethylcyclohexanemethanol,
preference is given to using amino-C.sub.2-C.sub.6-alkanols such as
2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol,
6-aminohexanol and also amino-C.sub.6-C.sub.6-cyloalkanols such as
aminocyclopentanol and aminocyclohexanol or mixtures thereof.
As diamino-C.sub.1-C.sub.8-alkane (component c4), preference is
given to using diamino-C.sub.4-C.sub.6-alkanes such as
1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane
(hexamethylenediamine, "HMD").
In a preferred embodiment, it is possible to use from 0.5 to 99.5
mol %, preferably from 0.5 to 50 mol %, of c3, based on the molar
amount of B, and from 0 to 50 mol %, preferably from 0 to 35 mol %,
of c4, based on the molar amount of B, for the preparation of the
partially aromatic polyesters.
The 2,2'-bisoxazolines c5 of the general formula III can generally
be obtained by the process from Angew. Chem. Int. Edit., Vol. 11
(1972), pp. 287-288. Particularly preferred bisoxazolines are those
in which R.sup.1 is a single bond, a (CH.sub.2).sub.z alkylene
group, where z=2, 3 or 4, e.g. methylene, ethane-1,2-diyl,
propane-1,3-diyl, propane-1,2-diyl, or a phenylene group. As
particularly preferred bisoxazolines, mention may be made of
2,2'-bis(2-oxazoline), bis(2-oxazolinyl)methane,
1,2-bis(2-oxazolinyl)ethane, 1,3-bis(2-oxazolinyl)propane or
1,4-bis(2-oxazolinyl)butane, in particular
1,4-bis(2-oxazolinyl)benzene, 1,2-bis(2-oxazolinyl)benzene or
1,3-bis(2-oxazolinyl)-benzene.
To prepare the partially aromatic polyesters, it is possible to
use, for example, from 70 to 98 mol % of B, up to 30 mol % of c3
and from 0.5 to 30 mol % of c4 and from 0.5 to 30 mol % of c5, in
each case based on the sum of the molar amounts of the components
B, c3, c4 and c5. In another preferred embodiment, it is possible
to use from 0.1 to 5% by weight, preferably from 0.2 to 4% by
weight, of c5, based on the total weight of A and B.
As component c6, it is possible to use natural aminocarboxylic
acids. These include valine, leucine, isoleucine, threonine,
methionine, phenylalanine, tryptophane, lysine, alanine, arginine,
aspartic acid, cysteine, glutamic acid, glycine, histidine,
proline, serine, tryosine, asparagine or glutamine.
Preferred aminocarboxylic acids of the general formulae IVa and IVb
are those in which s is an integer from 1 to 1000 and t is an
integer from 1 to 4, preferably 1 or 2, and T is selected from the
group consisting of phenylene and --(CH.sub.2).sub.u--, where u is
1, 5 or 12.
Furthermore, c6 can also be a polyoxazoline of the general formula
V. It is also possible for c6 to be a mixture of various
aminocarboxylic acids and/or polyoxazolines.
In a preferred embodiment, c6 can be used in amounts of from 0.01
to 50% by weight, preferably from 0.1 to 40% by weight, based on
the total amount of the components A and B.
Further components which can optionally by used for preparing the
partially aromatic polyesters include compounds d1 which comprise
at least three groups capable of ester formation.
The compounds d1 preferably comprise from three to ten functional
groups which are capable of forming ester bonds. Particularly
preferred compounds d1 have from three to six functional groups of
this type in the molecule, in particular from three to six hydroxyl
groups and/or carboxyl groups. Examples which may be mentioned
are:
tartaric acid, citric acid, malic acid;
trimethylolpropane, trimethylolethane;
pentaerythritol;
polyether triols;
glycerol;
trimesic acid;
trimellitic acid, trimellitic anhydride;
pyromellitic acid, pyromellitic dianhydride and
hydroxyisophthalic acid.
The compounds d1 are generally used in amounts of from 0.01 to 15
mol %, preferably from 0.05 to 10 mol %, particularly preferably
from 0.1 to 4 mol %, based on the component A.
As component d2, use is made of an isocyanate or a mixture of
various isocyanates. It is possible to use aromatic or aliphatic
diisocyanates. However, higher-functional isocyanates can also be
used.
An aromatic diisocyanate d2 is, for the purposes of the invention,
in particular
Tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate,
diphenylmethane 2,2'-diisocyanate, diphenylmethane
2,4'-diisocyanate, diphenylmethane 4,4'-diisocyanate, naphthylene
1,5-diisocyanate or xylylene diisocyanate.
Among these, particular preference is given to diphenylmethane
2,2'-, 2,4'- and 4,4'-diisocyanate as component d2. In general, the
latter diisocyanates are used as a mixture.
A possible three-ring isocyanate d2 is
tri(4-isocyanatophenyl)methane. The multiring aromatic
diisocyanates are obtained, for example, in the preparation of one-
or two-ring diisocyanates.
The component d2 can also comprise urethione groups, for example
for capping the isocyanate groups, in minor amounts, e.g. up to 5%
by weight, based on the total weight of the component d2.
For the purposes of the present invention, an aliphatic
diisocyanate d2 is, in particular, a linear or branched alkylene
diisocyanate or cycloalkylene diisocyanate having from 2 to 20
carbon atoms, preferably from 3 to 12 carbon atoms, e.g.
hexamethylene 1,6-diisocyanate, isophorone diisocyanate or
methylenebis(4-isocyanatocyclohexane). Particularly preferred
aliphatic diisocyanates d2 are hexamethylene 1,6-diisocyanate and
isophorone diisocyanate.
Preferred isocyanurates include the aliphatic isocyanurates derived
from alkylene diisocyanates or cycloalkylene diisocyanates having
from 2 to 20 carbon atoms, preferably from 3 to 12 carbon atoms,
e.g. isophorone diisocyanate or
methylenebis(4-isocyanatocyclohexane). The alkylene diisocyanates
can here be either linear or branched. Particular preference is
given to isocyanurates based on n-hexamethylene diisocyanate, for
example cyclic trimers, pentamers or higher oligomers of
n-hexamethylene diisocyanate.
The component d2 is generally used in amounts of from 0.01 to 5 mol
%, preferably from 0.05 to 4 mol %, particularly preferably from
0.1 to 4 mol %, based on the sum of the molar amounts of A and
B.
As divinyl ether d3, it is generally possible to use all customary
and commercially available divinyl ethers. Preference is given to
using 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether or
1,4-cyclohexanedimethanol divinyl ether or mixtures thereof.
The divinyl ethers are preferably used in amounts of from 0.01 to
5% by weight, in particular from 0.2 to 4% by weight, based on the
total weight of A and B.
Examples of preferred partially aromatic polyesters are based on
the following components
A, B, d1
A, B, d2
A, B, d1, d2
A, B, d3
A, B, c1
A, B, c1, d3
A, B, c3, c4
A, B, c3, c4, c5
A, B, d1, c3, c5
A, B, c3, d3
A, B, c3, d1
A, B, c1, c3, d3
A, B, c2
Among these, particular preference is given to partially aromatic
polyesters based on A, B, d1 or A, B, d2 or on A, B, d1, d2. In
another preferred embodiment, the partially aromatic polyesters are
based on A, B, c3, c4, c5 or A, B, d1, c3, c5.
The partially aromatic polyesters mentioned and the polyester
mixtures according to the invention are generally
biodegradable.
For the purposes of the present invention, the feature
"biodegradable" for a material or mixture of materials is present
when this material or mixture of materials has a percentage
biodegradation of at least 60% in at least one of the three methods
defined in DIN V 54900-2 (preliminary standard as at September
1998).
In general, the biodegradability leads to the polyester (mixtures)
decomposing in a period of time which is appropriate and can be
confirmed. Degradation can occur enzymatically, hydrolytically,
oxidatively and/or by action of electromagnetic radiation, for
example UV radiation, and can usually be brought about
predominantly by the action of microorganisms such as bacteria,
yeasts, fungi and algae. The biodegradability can be quantified by,
for example, mixing the polyester with compost and storing it for a
particular time. For example, in accordance with DIN EN 13432 or
DIN V 54900-2, method 3, CO.sub.2-free air is allowed to flow
through matured compost during composting and the compost is
subjected to a defined temperature program. Here, the
biodegradability is defined as percentage biodegradability via the
ratio of the net CO.sub.2 liberation from the sample (after
subtraction of the CO.sub.2 liberation by the compost without
sample) to the maximum CO.sub.2 liberation from the sample
(calculated from the carbon content of the sample). Biodegradable
polyester (mixtures) generally display significant degradation
phenomena such as growth of fungi and formation of cracks and holes
after only a few days of composting.
Other methods of determining the biodegradability are described,
for example, in ASTM D 5338 and ASTM D 6400.
The preparation of the partially aromatic polyesters is known per
se or can be carried out by known methods.
The preferred partially aromatic polyesters have a molecular weight
(M.sub.a) in the range from 1000 to 100 000 g/mol, in particular in
the range from 9000 to 75 000 g/mol, preferably in the range from
10 000 to 50 000 g/mol, and a melting point in the range from 60 to
170.degree. C., preferably in the range from 80 to 150.degree.
C.
The partially aromatic polyesters mentioned can have hydroxyl
and/or carboxyl end groups in any desired ratio. The partially
aromatic polyesters mentioned can also be end-group-modified. Thus,
for example, OH end groups can be acid-modified by reaction with
phthalic acid, phthalic anhydride, trimellitic acid, trimellitic
anhydride, pyromellitic acid or pyromellitic anhydride.
Suitable components ii of the biodegradable polyester mixtures are
basically homopolyesters or copolyesters selected from the group
consisting of polylactide, polycaprolactone, polyhydroxyalkanoates
and polyesters derived from aliphatic dicarboxylic acids and
aliphatic diols. Preferred components ii are polylactide (PLA) and
polyhydroxyalkanoates, in particular polyhydroxybutyrate (PHB),
polyhydroxybutyrate-co-valerate (PHBV). Products such as
NatureWorks.RTM. (polylactide from Cargill Dow), Biocycle.RTM.
(polyhydroxybutyrate from PHB Ind.); Enmat.RTM.
(polyhydroxybutyrate-co-valerate from Tianan) are of particular
importance.
The component iii according to the invention comprises a) a
copolymer which comprises epoxide groups and is based on styrene,
acrylic esters and/or methacrylic esters, b) a bisphenol A epoxide
or c) a natural oil, fatty acid ester or fatty acid amide
comprising epoxide groups.
Preference is given to using a copolymer which comprises epoxide
groups and is based on styrene, acrylic esters and/or methacrylic
esters. In general, the compounds have two or more epoxide groups
in the molecule. Oligomeric or polymeric epoxidized compounds, for
example, diglycidyl or polyglycidyl esters of dicarboxylic or
polycarboxylic acids or diglycidyl or polyglycidyl ethers of diols
or polyols or copolymers of styrene and glycidyl (meth)acrylates,
for example those marketed by Johnson Polymer under the trade name
Joncryl.RTM. ADR 4368, are particularly suitable.
Further preferred components iii are compounds which comprise at
least one carbon-carbon double or triple bond and at least one
epoxide group in the molecule. Glycidyl acrylate and glycidyl
methacrylate are particularly suitable.
Further preferred components iii) are c) (epoxidized) natural oils
or fatty acid esters comprising epoxide groups. Natural oils are,
for example, olive oil, linseed oil, soybean oil, palm oil, peanut
oil, coconut oil, tung oil, cod liver oil or a mixture of these
compounds. Particular preference is given to epoxidized soybean oil
(e.g. Merginat.RTM. ESBO from Hobum, Hamburg, or Edenol.RTM. B 316
from Cognis, Dusseldorf). The structure types a) and c) are
particularly preferably combined as component iii). As described in
more detail in the examples, the combination of Joncryl.RTM. ADR
4368 (structure type a)) and Merginat.RTM. ESBO (structure type c)
is particularly preferred.
Component iii) is used in an amount of from 0.1 to 15% by weight,
preferably from 0.1 to 10% by weight and particularly preferably
from 0.5 to 2% by weight, based on the total weight of the
components i) to ii), if mixtures are to be obtained.
The biodegradable polyester mixtures usually comprise from 5 to 90%
by weight, preferably from 10 to 85% by weight, particularly
preferably from 15 to 80% by weight, in particular from 40 to 60%
by weight, of component i and from 10 to 95% by weight, preferably
from 15 to 80% by weight, particularly preferably from 40 to 80% by
weight, very particularly preferably from 40 to 60% by weight, of
component ii, where the percentages by weight are in each case
based on the total weight of the components i to ii and add up to
100% by weight.
Polyester mixtures having a high polyhydroxybutyrate (PHB) or in
particular polylactide (PLA) content (component ii) can be used for
the production of moldings by, for example, injection molding.
Mixtures of from 60 to 95% by weight of component can usually be
realized here. An improved process for producing impact-modified
molding compositions is described under the production
processes.
If a polyester comprising sebacic acid or mixtures of sebacic acid
with adipic acid as dicarboxylic acid (component a1)) are used as
component i), the proportion of the polyester in the mixtures with
component ii) can even be reduced below the 10% by weight
limit.
The biodegradable polyester mixtures usually further comprise from
0.1 to 15% by weight, preferably from 0.5 to 10% by weight,
particularly preferably from 1 to 5% by weight, of component iii,
where the percentages by weight are in each case based on the total
weight of the components i to ii.
The biodegradable polyester mixtures can comprise further
constituents which are known to those skilled in the art but are
not essential for the invention. Examples are the additives
customary in plastics technology, e.g. stabilizers, neutralizing
agents, lubricants and release agents, antiblocking agents, dyes or
fillers. In addition, these naturally comprise a metal-organic
framework as additive.
The production of the biodegradable polyester mixtures of the
invention from the individual components can be carried out by
known methods (EP 792 309 and U.S. Pat. No. 5,883,199).
For example, all components I, ii and iii can be mixed and reacted
at elevated temperatures, for example from 120.degree. C. to
250.degree. C., in one process step in mixing apparatuses known to
those skilled in the art, for example kneaders or extruders. The
reaction is preferably carried out in the presence of a
free-radical initiator.
An illustrative process for producing the biodegradable polyester
mixtures can comprise the following steps:
In a first step, from 1 to 50% by weight, preferably from 5 to 35%
by weight, of component iii is mixed with from 50 to 99% by weight,
preferably from 65 to 95% by weight, of component i at temperatures
of from 110 to 145.degree. C., preferably from 120 to 140.degree.
C., to give a brancher masterbatch. At these temperatures, a
homogeneous blend is obtained without an appreciable increase in
the molecular weight occurring. The brancher masterbatch obtained
in this way can be stored without problems at room temperature. In
a second step, the desired composition can be obtained by addition
of the brancher masterbatch and, if appropriate, further component
i to component ii. This compounding step is carried out at from 150
to 250.degree. C., preferably from 160 to 190.degree. C.
The temperatures in the compounding step can generally be reduced,
and decomposition of sensitive biopolymers such as
polyhydroxybutyrates can be avoided as a result, by using an
activator selected from the group consisting of zinc, tin, titanium
compound and C.sub.1-C.sub.12-alkyltriphenylphosphonium halide.
Typical brancher masterbatches comprise from 5 to 35% by weight,
preferably from 10 to 20% by weight, of component iii) and from 65
to 95% by weight, preferably from 80 to 90% by weight, of component
i. These brancher masterbatches have surprisingly been found to be
advantageous compared to corresponding brancher masterbatches
comprising components ii) and iii). The brancher masterbatches are
provided by the present invention. It is clear from examples 4 to 6
described below that the brancher masterbatches according to the
invention comprising the components i) and iii) have advantages
over the sometimes commercially available brancher masterbatches
(e.g. polylactide and glycidyl methacrylate) in terms of the flow
rate of the polyester mixtures formed. In addition, the brancher
masterbatches of the invention have excellent storage
stability.
Examples of brancher masterbatches according to the invention
are:
component i), polyester prepared by condensation of:
adipic acid/terephthalic acid and 1,4-butanediol (e.g. Ecoflex.RTM.
FBX 7011); adipic acid/terephthalic acid and 1,3-propanediol;
succinic acid/terephthalic acid and 1,4-butanediol; succinic
acid/terephthalic acid and 1,3-propanediol; sebacic
acid/terephthalic acid and 1,4-butanediol; sebacic
acid/terephthalic acid and 1,3-propanediol; azelaic
acid/terephthalic acid and 1,4-butanediol; brassylic
acid/terephthalic acid and 1,4-butanediol; and component iii):
glycidyl methacrylate (e.g. Joncryl.RTM. ADR 4368 from Johnson
Polymer).
To produce polyester mixtures having a high proportion of "hard" or
"brittle" component ii), for example >50% by weight of
polyhydroxybutyrate or in particular polylactide, the following
procedure has been found to be particularly advantageous. An
intermediate compound which preferably comprises from 48 to 60% by
weight of component i), from 40 to 50% by weight of component ii)
and from 0.5 to 2% by weight of component iii) is produced as
described above either by mixing the components i), ii) and iii) or
in two steps by mixing one of the abovementioned brancher
masterbatches with component ii) and, if appropriate, further
component i). In an additional step, this intermediate compound is
admixed with further component ii) until the desired content of
component ii) in the polyester mixture has been attained. The
polyester mixture produced by this three-stage process is very
suitable for producing biodegradable, impact-modified polyester
mixtures.
Sebacic acid or a mixture of sebacic acid with adipic acid is
preferably used as aliphatic dicarboxylic acid when polymer
mixtures having a high proportion of "hard" or "brittle" component
ii), for example polyhydroxybutyrate or in particular polylactide,
are produced.
On the basis of experience with other compounds (e.g. development
of Ecoflex/starch compounds), the solution formulation was varied
by use of a compatibilizer. Instead of incorporating this into the
total matrix in a costly fashion, only part of the Ecoflex/PLA
formulation is provided with a compatibilizer concentrate. Examples
of such a compatibilizer masterbatch are the abovementioned
brancher masterbatches and intermediate compounds. This saves
compounding costs: 9.5-89.5% by weight of Ecoflex, 89.5-9.5% by
weight of PLA, 0.5-20% by weight of compatibilizer masterbatch,
0-15% by weight of additives (e.g. palmitates, laurates, stearates,
PEG) and from 0 to 50% by weight of fillers (chalk, talc, kaolin,
silica, etc.); 29.5-59.5% by weight of Ecoflex, 59.5-29.5% by
weight of PLA, 0.5-20% by weight of compatibilizer masterbatch,
0-15% by weight of additives (e.g. palmitates, laurates, stearates,
PEG) and from 0 to 50% by weight of fillers (chalk, talc, kaolin,
silica).
The biodegradable polyester mixtures are particularly suitable for
producing moldings, foils or fibers. These can be produced by
methods known to those skilled in the art.
The biodegradable polyester mixtures give biodegradable polymer
mixtures which can be processed without problems (good bubble
stability) to give puncture-resistant foils.
The biodegradable material comprises at least one porous
metal-organic framework as additive. This can be introduced by
customary methods during the processing of the biodegradable
material to produce foils or films.
Such metal-organic frameworks (MOFs) are known in the prior art and
are described, for example, in U.S. Pat. No. 5,648,508, EP-A-0 790
253, M. O'Keeffe et al., J. Sol. State Chem., 152 (2000), pages 3
to 20, H. Li et al., Nature 402, (1999), page 276, M. Eddaoudi et
al., Topics in Catalysis 9, (1999), pages 105 to 111, B. Chen et
al., Science 291, (2001), pages 1021 to 1023, DE-A 101 11 230, DE-A
10 2005 053430, WO-A 2007/054581, WO-A 2005/049892 and WO-A
2007/023134.
As a specific group of these metal-organic frameworks, "limited"
frameworks in which the framework does not extend infinitely but
forms polyhedra as a result of a specific choice of the organic
compound are described in the most recent literature. A. C. Sudik,
et al., J. Am. Chem. Soc. 127 (2005), 7110-7118, describes such
particular frameworks. These are described to distinguish them from
other frameworks, as metal-organic polyhedra (MOP).
A further specific group of porous metal-organic frameworks are
those in which the organic compound as ligand is a monocyclic,
bicyclic or polycyclic ring system which is derived from at least
one heterocycle selected from the group consisting of pyrrole,
alpha-pyridone and gamma-pyridone and has at least two nitrogen
atoms in the ring. The electrochemical preparation of such
frameworks is described in WO-A 2007/131955.
The general suitability of metal-organic frameworks for the
absorption of gases and liquids is described, for example, in WO-A
2005/003622 and EP-A 1 702 925.
These specific groups are particularly suitable for the purposes of
the present invention.
The metal-organic frameworks according to the present invention
comprise pores, in particular micropores and/or mesopores.
Micropores are defined as pores having a diameter of 2 nm or less
and mesopores are defined by a diameter in the range from 2 to 50
nm, in each case in accordance with the definition given in Pure
& Applied Chem. 57 (1983), 603-619, in particular on page 606.
The presence of micropores and/or mesopores can be checked by means
of sorption measurements, with these measurements determining the
uptake capacity of the MOF for nitrogen at 77 kelvin in accordance
with DIN 66131 and/or DIN 66134.
The specific surface area, calculated according to the Langmuir
model (DIN 66131, 66134) of an MOF in powder form is preferably
more than 100 m.sup.2/g, more preferably above 300 m.sup.2/g, more
preferably more than 700 m.sup.2/g, even more preferably more than
800 m.sup.2/g, even more preferably more than 1000 m.sup.2/g and
particularly preferably more than 1200 m.sup.2/g.
Shaped bodies comprising metal-organic frameworks can have a lower
active surface area; but preferably more than 150 m.sup.2/g, more
preferably more than 300 m.sup.2/g, even more preferably more than
700 m.sup.2/g.
The metal component in the framework according to the present
invention is preferably selected from groups Ia, IIa, IIIa, IVa to
VIIIa and Ib to VIb. Particular preference is given to Mg, Ca, Sr,
Ba, Sc, Y, Ln, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro,
Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl,
Si, Ge, Sn, Pb, As, Sb and Bi, where Ln represents the
lanthanides.
Lanthanides are La, Ce, Pr, Nd, Pm, Sm, En, Gd, Tb, Dy, Ho, Er, Tm,
Yb.
With regard to the ions of these elements, particular mention may
be made of Mg.sup.2+, Ca.sup.2+, Sr.sup.2+, Ba.sup.2+, Sc.sup.3+,
Y.sup.3+, Ln.sup.3+, Ti.sup.4+, Zr.sup.4+, Hf.sup.4+, V.sup.4+,
V.sup.3+, V.sup.2+, Nb.sup.3+, Ta.sup.3+, Cr.sup.3+, Mo.sup.3+,
W.sup.3+, Mn.sup.3+, Mn.sup.2+, Re.sup.3+, Re.sup.2+, Fe.sup.3+,
Fe.sup.2+, Ru.sup.3+, Ru.sup.2+, Os.sup.3+, Os.sup.2+, Co.sup.3+,
Co.sup.2+, Rh.sup.2+, Rh.sup.+, Ir.sup.2+, Ni.sup.2+, Ni.sup.+,
Pd.sup.2+, Pd.sup.+, Pt.sup.2+, Pt.sup.+, Cu.sup.2+, Cu.sup.+,
Ag.sup.+, Au.sup.+, Zn.sup.2+, Cd.sup.2+, Hg.sup.2+, Al.sup.3+,
Ga.sup.3+, In.sup.3+, Tl.sup.3+, Si.sup.4+, Si.sup.2+, Ge.sup.4+,
Ge.sup.2+, Sn.sup.4+, Sn.sup.2+, Pb.sup.4+, Pb.sup.2+, As.sup.5+,
As.sup.3+, As.sup.+, Sb.sup.5+, Sb.sup.3+, Sb.sup.+, Bi.sup.5+,
Bi.sup.3+ and Bi.sup.+.
Furthermore, particular preference is given to Mg, Al, Y, Sc, Zr,
Ti, V, Cr, Mo, Fe, Co, Cu, Ni, Zn, Ln. Greater preference is given
to Al, Mo, Y, Sc, Mg, Fe, Cu and Zn. Particular preference is given
to Sc, Al, Cu and Zn. Particular preference is given to Cu.
Owing to the use of biodegradable foils or films, particular
preference is given to the metals used in the metal-organic
framework likewise being biologically acceptable. Particular
mention may here be made of Mg, Ca and Al.
The term "at least bidentate organic compound" refers to an organic
compound which comprises at least one functional group which is
able to form at least two coordinate bonds to a given metal ion
and/or a coordinate bond to each of two or more, preferably two,
metal atoms.
As functional groups via which the coordinate bonds mentioned can
be formed, particular mention may be made of, for example, the
following functional groups: --CO.sub.2H, --CS.sub.2H, --NO.sub.2,
--B(OH).sub.2, --SO.sub.3H, --Si(OH).sub.3, --Ge(OH).sub.3,
--Sn(OH).sub.3, --Si(SH).sub.4, --Ge(SH).sub.4, --Sn(SH).sub.3,
--PO.sub.3H, --AsO.sub.3H, --AsO.sub.4H, --P(SH).sub.3,
--As(SH).sub.3, --CH(RSH).sub.2, --C(RSH).sub.3,
--CH(RNH.sub.2).sub.2, --C(RNH.sub.2).sub.3, --CH(ROH).sub.2,
--C(ROH).sub.3, --CH(RCN).sub.2, --C(RCH).sub.3, where R is, for
example, preferably an alkylene group having 1, 2, 3, 4 or 5 carbon
atoms, for example a methylene, ethylene, n-propylene, i-propylene,
n-butylene, i-butylene, tert-butylene or n-pentylene group, or an
aryl group comprising 1 or 2 aromatic rings, for example 2C.sub.6
rings, which may, if appropriate, be fused and may be independently
substituted by at least one substituent in each case and/or may
comprise, independently of one another, at least one heteroatom
such as N, O and/or S. In likewise preferred embodiments,
functional groups in which the above-mentioned radical R is not
present are possible. Such groups are, inter alia, --CH(SH).sub.2,
--C(SH).sub.3, --CH(NH.sub.2).sub.2, --C(NH.sub.2).sub.3,
--CH(OH).sub.2, --C(OH).sub.3, --CH(CN).sub.2 or --C(CN).sub.3.
However, the functional groups can also be heteroatoms of a
heterocycle. Particular mention may here be made of nitrogen
atoms.
The at least two functional groups can in principle be any suitable
organic compound, as long as it is ensured that the organic
compound in which these functional groups are present is capable of
forming the coordinate bond and of producing the framework.
The organic compounds which comprise the at least two functional
groups are preferably derived from a saturated or unsaturated
aliphatic compound or an aromatic compound or a both aliphatic and
aromatic compound.
The aliphatic compound or the aliphatic part of the both aliphatic
and aromatic compound can be linear and/or branched and/or cyclic,
with a plurality of rings per compound also being possible. More
preferably, the aliphatic compound or the aliphatic part of the
both aliphatic and aromatic compound comprises from 1 to 15, more
preferably from 1 to 14, more preferably from 1 to 13, more
preferably from 1 to 12, more preferably from 1 to 11 and
particularly preferably from 1 to 10, carbon atoms, for example 1,
2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Particular preference is
here given to, inter alia, methane, adamantane, acetylene, ethylene
or butadiene.
The aromatic compound or the aromatic part of the both aromatic and
aliphatic compound can have one or more rings, for example two,
three, four or five rings, with the rings being able to be separate
from one another and/or at least two rings being able to be present
in fused form. The aromatic compound or the aromatic part of the
both aliphatic and aromatic compound particularly preferably has
one, two or three rings, with one or two rings being particularly
preferred. Furthermore, each ring of the specified compound can
independently comprise at least one heteroatom such as N, O, S, B,
P, Si, Al, preferably N, O and/or S. The aromatic compound or the
aromatic part of the both aromatic and aliphatic compound more
preferably comprises one or two C.sub.6 rings which are present
either separately or in fused form. Particular mention may be made
of benzene, naphthalene and/or biphenyl and/or bipyridyl and/or
pyridyl as aromatic compounds.
The at least bidentate organic compound is more preferably an
aliphatic or aromatic, acyclic or cyclic hydrocarbon which has from
1 to 18, preferably from 1 to 10 and in particular 6, carbon atoms
and additionally has exclusively 2, 3 or 4 carboxyl groups as
functional groups.
For example, the at least bidentate organic compound is derived
from a dicarboxylic acid such as oxalic acid, succinic acid,
tartaric acid, 1,4-butanedicarboxylic acid, 1,4-butenedicarboxylic
acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic
acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid,
1,9-heptadecane-dicarboxylic acid, heptadecanedicarboxylic acid,
acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid,
1,3-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid,
pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic
acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid,
imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic
acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic
acid, 6-chloroquinoxaline-2,3-dicarboxylic acid,
4,4'-diaminophenylmethane-3,3'-dicarboxylic acid,
quinoline-3,4-dicarboxylic acid,
7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid,
diimidecarboxylic acid, pyridine-2,6-dicarboxylic acid,
2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic
acid, 2-isopropylimidazole-4,5-dicarboxylic acid,
tetrahydropyrane-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic
acid, perylenedicarboxylic acid, Pluriol E 200-dicarboxylic acid,
3,6-dioxaoctanedicarboxylic acid,
3,5-cyclohexadiene-1,2-dicarboxylic acid, octadicarboxylic acid,
pentane-3,3-carboxylic acid,
4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid,
4,4'-diaminodiphenyl-3,3'-dicarboxylic acid,
benzidine-3,3'-dicarboxylic acid,
1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid,
1,1'-dinaphthyldicarboxylic acid,
7-chloro-8-methylquinoline-2,3-dicarboxylic acid,
1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran
250-dicarboxylic acid,
1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid,
7-chloroquinoline-3,8-dicarboxylic acid,
1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic
acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid,
phenylindanedicarboxylic acid,
1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic
acid, 2,-benzoylbenzene-1,3-dicarboxylic acid,
1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid,
2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic
acid, 3,6,9-trioxaundecanedicarboxylic acid,
hydroxybenophenonedicarboxylic acid, Pluriol E 300-dicarboxylic
acid, Pluriol E 400-dicarboxylic acid, Pluriol E 600-dicarboxylic
acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic
acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid,
4,4'-diamino(diphenyl ether)diimide-dicarboxylic acid,
4,4'-diaminodiphenylmethanediimidedicarboxylic acid,
4,4'-diamino(diphenyl sulfone)diimidedicarboxylic acid,
1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid,
1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid,
2,3-naphthalenedicarboxylic acid,
8-methoxy-2,3-naphthalenedicarboxylic acid,
8-nitro-2,3-naphthalenecarboxylic acid,
8-sulfo-2,3-naphthalenedicarboxylic acid,
anthracene-2,3-dicarboxylic acid,
2',3'-diphenyl-p-ter-phenyl-4,4''-dicarboxylic acid, (diphenyl
ether)-4,4'-dicarboxylic acid, imidazole-4,5-di-carboxylic acid,
4(1H)-oxothiochromene-2,8-dicarboxylic acid,
5-tert-butyl-1,3-benzene-dicarboxylic acid,
7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid,
4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic
acid, tetra-decanedicarboxylic acid, 1,7-heptadicarboxylic acid,
5-hydroxy-1,3-benzene-dicarboxylic acid,
2,5-dihydroxy-1,4-dicarboxylic acid, pyrazine-2,3-dicarboxylic
acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid,
eicosenedicarboxylic acid,
4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid,
1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic
acid, 2,5-pyridinedicarboxylic acid, cyclo-hexene-2,3-dicarboxylic
acid, 2,9-dichlorofluorubin-4,11-dicarboxylic acid,
7-chloro-3-methylquinoline-6,8-dicarboxylic acid,
2,4-dichlorobenzophenone-2',5'-dicarboxylic acid,
1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid,
1-methylpyrrole-3,4-dicarboxylic acid,
1-benzyl-1H-pyrrole-3,4-dicarboxylic acid,
anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid,
2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic
acid, cyclobutane-1,1-dicarboxylic acid,
1,14-tetra-decanedicarboxylic acid,
5,-6-dehydronorbornane-2,3-dicarboxylic acid,
5-ethyl-2,3-pyridinedicarboxylic acid or camphordicarboxylic
acid.
Furthermore, the at least bidentate organic compound is more
preferably one of the dicarboxylic acids mentioned by way of
example above as such.
For example, the at least bidentate organic compound can be derived
from a tricarboxylic acid such as
2-hydroxy-1,2,3-propanetricarboxylic acid,
7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,3-,
1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid,
2-phosphono-1,2,4-butanetricarboxylic acid,
1,3,5-benzenetricarboxylic acid,
1-hydroxy-1,2,3-propanetricarboxylic acid,
4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-F]quinoline-2,7,9-tricarboxylic
acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid,
3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid,
1,2,3-propanetricarboxylic acid or aurintricarboxylic acid.
Furthermore, the at least bidentate organic compound is more
preferably one of the tricarboxylic acids mentioned by way of
example above as such.
Examples of an at least bidentate organic compound derived from a
tetracarboxylic acid are
1,1-dioxidoperylo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid,
perylenetetracarboxylic acids such as
perylene-3,4,9,10-tetracarboxylic acid or (perylene
1,12-sulfone)-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic
acids such as 1,2,3,4-butanetetracarboxylic acid or
meso-1,2,3,4-butanetetracarboxylic acid,
decane-2,4,6,8-tetracarboxylic acid,
1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic
acid, 1,2,4,5-benzenetetracarboxylic acid,
1,2,11,12-dodecanetetracarboxylic acid,
1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic
acid, 1,4,5,8-naphthalenetetracarboxylic acid,
1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic
acid, 3,3',4,4'-benzophenonetetracarboxylic acid,
tetrahydrofurantetracarboxylic acid or cyclopentanetetracarboxylic
acids such as cyclopentane-1,2,3,4-tetracarboxylic acid.
Furthermore, the at least bidentate organic compound is more
preferably one of the tetracarboxylic acids mentioned by way of
example above as such.
Preferred heterocycles as at least bidentate organic compounds
which form a coordinate bond via the ring heteroatoms are the
following substituted or unsubstituted ring systems:
##STR00005## ##STR00006## ##STR00007##
Very particular preference is given to optionally at least
monosubstituted aromatic dicarboxylic, tricarboxylic or
tetracarboxylic acids having one, two, three, four or more rings,
with each of the rings being able to comprise at least one
heteroatom and two or more rings being able to comprise identical
or different heteroatoms. For example, preference is given to
one-ring dicarboxylic acids, one-ring tricarboxylic acids, one-ring
tetracarboxylic acids, two-ring dicarboxylic acids, two-ring
tricarboxylic acids, two-ring tetracarboxylic acids, three-ring
dicarboxylic acids, three-ring tricarboxylic acids, three-ring
tetracarboxylic acids, four-ring dicarboxylic acids, four-ring
tricarboxylic acids and/or four-ring tetracarboxylic acids.
Suitable heteroatoms are, for example, N, O, S, B, P, and preferred
heteroatoms are N, S and/or O, Suitable substituents here are,
inter alia, --OH, a nitro group, an amino group and an alkyl or
alkoxy group.
Particularly preferred at least bidentate organic compounds are
imidazolates such as 2-methylimidazolate, are acetylenedicarboxylic
acid (ADC), camphordicarboxylic acid, fumaric acid, succinic acid,
benzenedicarboxylic acids, such as phthalic acid, isophthalic acid,
terephthalic acid (BDC), aminoterephthalic acid, triethylenediamine
(TEDA), naphthalenedicarboxylic acids (NDC), biphenyldicarboxylic
acids such as 4,4'-biphenyldicarboxylic acid (BPDC),
pyrazinedicarboxylic acids such as 2,5-pyrazinedicarboxylic acid,
bipyridinedicarboxylic acids such as 2,2'-bipyridine-dicarboxylic
acids such as 2,2'-bipyridine-5,5'-dicarboxylic acid,
benzenetricarboxylic acids such as 1,2,3-,
1,2,4-benzenetricarboxylic acid or 1,3,5-benzenetricarboxylic acid
(BTC), benzenetetracarboxylic acid, adamantanetetracarboxylic acid
(ATC), adamantanedibenzoate (ADB), benzenetribenzoate (BTB),
methanetetrabenzoate (MTB), adamanantetrabenzoate or
dihydroxyterephthalic acids such as 2,5-dihydroxy-terephthalic acid
(DHBDC), tetrahydropyrene-2,7-dicarboxylic acid (HPDC),
biphenyltetracarboxylic acid (BPTC), 1,3-bis(4-pyridyl)propane
(BPP).
Very particular preference is given to using, inter alia,
2-methylimidazole, 2-ethylimidazole, phthalic acid, isophthalic
acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid,
1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid,
1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid,
1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic
acid, aminoBDC, TEDA, fumaric acid, biphenyldicarboxylate, 1,5- and
2,6-naphthalenedicarboxylic acid, tert-butylisophthalic acid,
dihydroxybenzoic acid, BTB, HPDC, BPTC, BPP.
Apart from these at least bidentate organic compounds, the
metal-organic framework can also comprise one or more monodentate
ligands and/or one or more at least bidentate ligands which are not
derived from a dicarboxylic, tricarboxylic or tetracarboxylic
acid.
Apart from these at least bidentate organic compounds, the
metal-organic framework can also comprise one or more monodentate
ligands.
Owing to the use in biodegradable foils or films, preferred at
least bidentate organic compounds are formic acid, acetic acid or
an aliphatic dicarboxylic or polycarboxylic acid, for example
malonic acid, fumaric acid or the like or compounds derived from
these.
For the purposes of the present invention, the term "derived" means
that the at least one at least bidentate organic compound is
present in partially or completely deprotonated form. Furthermore,
the term "derived" means that the at least one at least bidentate
organic compound can have further substituents. Thus, a
dicarboxylic or polycarboxylic acid can have, in addition to the
carboxylic acid function, one or more independent substituents such
as amino, hydroxyl, methoxy, halogen or methyl groups. Preference
is given to no further substituent being present. For the purposes
of the present invention, the term "derived" also means that the
carboxylic acid function can be present as a sulfur analogue.
Sulfur analogues are --C(.dbd.O)SH and also its tautomer and
--C(S)SH.
Suitable solvents for preparing the metal-organic framework are,
inter alia, ethanol, dimethylformamide, toluene, methanol,
chlorobenzene, diethylformamide, dimethyl sulfoxide, water,
hydrogen peroxide, methylamine, sodium hydroxide solution,
N-methylpyrrolidone ether, acetonitrile, benzyl chloride,
triethylamine, ethylene glycol and mixtures thereof. Further metal
ions, at least bidentate organic compounds and solvents for the
preparation of MOFs are described, inter alia, in U.S. Pat. No.
5,648,508 or DE-A 101 11 230.
The pore size of the metal-organic framework can be controlled by
selection of the appropriate ligand and/or the at least bidentate
organic compound. In general, the larger the organic compound, the
larger the pore size. The pore size is preferably from 0.2 nm to 30
nm, particularly preferably in the range from 0.3 nm to 3 nm, based
on the crystalline material.
However, larger pores whose size distribution can vary also occur
in a shaped body comprising a metal-organic framework. Preference
is, however, given to more than 50% of the total pore volume, in
particular more than 75%, being made up by pores having a pore
diameter of up to 1000 mm. However, preference is given to a major
part of the pore volume being made up by pores having two diameter
ranges. It is therefore preferred for more than 25% of the total
pore volume, in particular more than 50% of the total pore volume,
to be made up by pores which have a diameter in the range from 100
nm to 800 nm and more than 15% of the total pore volume, in
particular more than 25% of the total pore volume, to be made up by
pores which have a diameter up to 10 nm. The pore distribution can
be determined by means of mercury porosimetry.
The particle size in the foil or the film can be adapted according
to known methods.
Examples of metal-organic frameworks are given below. The
designation of the framework, the metal and the at least bidentate
ligand and also the solvent and the cell parameters (angles
.alpha., .beta. and .gamma. and the dimensions A, B and C in A) are
indicated. The latter were determined by X-ray diffraction.
TABLE-US-00001 Constituents molar ratio Space MOF-n M + L Solvents
.alpha. .beta. .gamma. a b c group MOF-0
Zn(NO.sub.3).sub.2.cndot.6H.sub.2O ethanol 90 90 120 16.711 16.711
1- 4.189 P6(3)/ H.sub.3(BTC) Mcm MOF-2
Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DMF 90 102.8 90 6.718 15.49
12.43- P2(1)/n (0.246 mmol) toluene H.sub.2(BDC) 0.241 mmol) MOF-3
Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DMF 99.72 111.11 108.4 9.726
9.91- 1 10.45 P-1 (1.89 mmol) MeOH H.sub.2(BDC) (1.93 mmol) MOF-4
Zn(NO.sub.3).sub.2.cndot.6H.sub.2O ethanol 90 90 90 14.728 14.728
14- .728 P2(1)3 (1.00 mmol) H.sub.3(BTC) (0.5 mmol) MOF-5
Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DMF 90 90 90 25.669 25.669
25.669- Fm-3m (2.22 mmol) chloro- H.sub.2(BDC) benzene (2.17 mmol)
MOF-38 Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DMF 90 90 90 20.657
20.657 17.84- I4cm (0.27 mmol) chloro- H.sub.3(BTC) benzene (0.15
mmol) MOF-31 Zn(NO.sub.3).sub.2.cndot.6H.sub.2O ethanol 90 90 90
10.821 10.821 1- 0.821 Pn(-3)m Zn(ADC).sub.2 0.4 mmol H.sub.2(ADC)
0.8 mmol MOF-12 Zn(NO.sub.3).sub.2.cndot.6H.sub.2O ethanol 90 90 90
15.745 16.907 1- 8.167 Pbca Zn.sub.2(ATC) 0.3 mmol H.sub.4(ATC)
0.15 mmol MOF-20 Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DMF 90 92.13 90
8.13 16.444 12.8- 07 P2(1)/c ZnNDC 0.37 mmol chloro- H.sub.2NDC
benzene 0.36 mmol MOF-37 Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DEF
72.38 83.16 84.33 9.952 11.5- 76 15.556 P-1 0.2 mmol chloro
H.sub.2NDC benzene 0.2 mmol MOF-8
Tb(NO.sub.3).sub.3.cndot.5H.sub.2O DMSO 90 115.7 90 19.83 9.822
19.1- 83 C2/c Tb.sub.2(ADC) 0.10 mmol MeOH H.sub.2ADC 0.20 mmol
MOF-9 Tb(NO.sub.3).sub.3.cndot.5H.sub.2O DMSO 90 102.09 90 27.056
16.795 2- 8.139 C2/c Tb.sub.2(ADC) 0.08 mmol H.sub.2ADB 0.12 mmol
MOF-6 Tb(NO.sub.3).sub.3.cndot.5H.sub.2O DMF 90 91.28 90 17.599
19.996 10.- 545 P21/c 0.30 mmol MeOH H.sub.2(BDC) 0.30 mmol MOF-7
Tb(NO.sub.3).sub.3.cndot.5H.sub.2O H.sub.2O 102.3 91.12 101.5 6.142
- 10.069 10.096 P-1 0.15 mmol H.sub.2(BDC) 0.15 mmol MOF-69A
Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DEF 90 111.6 90 23.12 20.92 12 -
C2/c 0.083 mmol H.sub.2O.sub.2 4,4'BPDC MeNH.sub.2 0.041 mmol
MOF-69B Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DEF 90 95.3 90 20.17
18.55 12.1- 6 C2/c 0.083 mmol H.sub.2O.sub.2 2,6-NCD MeNH.sub.2
0.041 mmol MOF-11 Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O H.sub.2O 90
93.86 90 12.987 11- .22 11.336 C2/c Cu.sub.2(ATC) 0.47 mmol
H.sub.2ATC 0.22 mmol MOF-11 90 90 90 8.4671 8.4671 14.44 P42/
Cu.sub.2(ATC) mmc dehydr. MOF-14
Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O H.sub.2O 90 90 90 26.946
26.94- 6 26.946 Im-3 Cu.sub.3(BTB) 0.28 mmol DMF H.sub.3BTB EtOH
0.052 mmol MOF-32 Cd(NO.sub.3).sub.2.cndot.4H.sub.2O H.sub.2O 90 90
90 13.468 13.468 - 13.468 P(-4)3m Cd(ATC) 0.24 mmol NaOH H.sub.4ATC
0.10 mmol MOF-33 ZnCl.sub.2 H.sub.2O 90 90 90 19.561 15.255 23.404
Imma Zn.sub.2(ATB) 0.15 mmol DMF H.sub.4ATB EtOH 0.02 mmol MOF-34
Ni(NO.sub.3).sub.2.cndot.6H.sub.2O H.sub.2O 90 90 90 10.066 11.163
- 19.201 P2.sub.12.sub.12.sub.1 Ni(ATC) 0.24 mmol NaOH H.sub.4ATC
0.10 mmol MOF-36 Zn(NO.sub.3).sub.2.cndot.4H.sub.2O H.sub.2O 90 90
90 15.745 16.907 - 18.167 Pbca Zn.sub.2(MTB) 0.20 mmol DMF
H.sub.4MTB 0.04 mmol MOF-39 Zn(NO.sub.3).sub.24H.sub.2O H.sub.2O 90
90 90 17.158 21.591 25.308 - Pnma Zn.sub.3O(HBTB) 0.27 mmol DMF
H.sub.3BTB EtOH 0.07 mmol NO305 FeCl.sub.2.cndot.4H.sub.2O DMF 90
90 120 8.2692 8.2692 63.566 R-3c 5.03 mmol formic acid 86.90 mmol
NO306A FeCl.sub.2.cndot.4H.sub.2O DEF 90 90 90 9.9364 18.374 18.374
Pbcn 5.03 mmol formic acid 86.90 mmol NO29
Mn(Ac).sub.2.cndot.4H.sub.2O DMF 120 90 90 14.16 33.521 33.521 P-1
MOF-0 0.46 mmol similar H.sub.3BTC 0.69 mmol BPR48
Zn(NO.sub.3).sub.26H.sub.2O DMSO 90 90 90 14.5 17.04 18.02 Pbca A2
0.012 mmol toluene H.sub.2BDC 0.012 mmol BPR69
Cd(NO.sub.3).sub.24H.sub.2O DMSO 90 98.76 90 14.16 15.72 17.66 Cc
B1 0.0212 mmol H.sub.2BDC 0.0428 mmol BPR92
Co(NO.sub.3).sub.2.cndot.6H.sub.2O NMP 106.3 107.63 107.2 7.5308
10.- 942 11.025 P1 A2 0.018 mmol H.sub.2BDC 0.018 mmol BPR95
Cd(NO.sub.3).sub.24H.sub.2O NMP 90 112.8 90 14.460 11.085 15.829
P2(- 1)/n C5 0.012 mmol H.sub.2BDC 0.36 mmol
CuC.sub.6H.sub.4O.sub.6 Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O DMF 90
105.29- 90 15.259 14.816 14.13 P2(1)/c 0.370 mmol chlorobenzene
H.sub.2BDC(OH).sub.2 0.37 mmol M(BTC) Co(SO.sub.4) H.sub.2O DMF as
for MOF-0 MOF-0 0.055 mmol similar H.sub.3BTC 0.037 mmol
Tb(C.sub.6H.sub.4O.sub.6) Tb(NO.sub.3).sub.3.cndot.5H.sub.2O DMF
104.6 107- .9 97.147 10.491 10.981 12.541 P-1 0.370 mmol
chlorobenzene H.sub.2(C.sub.6H.sub.4O.sub.6) 0.56 mmol
Zn(C.sub.2O.sub.4) ZnCl.sub.2 DMF 90 120 90 9.4168 9.4168 8.464
P(-3)1m 0.370 mmol chlorobenzene oxalic acid 0.37 mmol Co(CHO)
Co(NO.sub.3).sub.2.cndot.5H.sub.2O DMF 90 91.32 90 11.328 10.049 1-
4.854 P2(1)/n 0.043 mmol formic acid 1.60 mmol Cd(CHO)
Cd(NO.sub.3).sub.2.cndot.4H.sub.2O DMF 90 120 90 8.5168 8.5168 22.-
674 R-3c 0.185 mmol formic acid 0.185 mmol
Cu(C.sub.3H.sub.2O.sub.4) Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O DMF
90 90 9- 0 8.366 8.366 11.919 P43 0.043 mmol malonic acid 0.192
mmol Zn.sub.6(NDC).sub.5 Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DMF 90
95.902 90 19- .504 16.482 14.64 C2/m MOF-48 0.097 mmol
chlorobenzene 14 NDC H.sub.2O.sub.2 0.069 mmol MOF-47
Zn(NO.sub.3).sub.26H.sub.2O DMF 90 92.55 90 11.303 16.029 17.535
P2- (1)/c 0.185 mmol chlorobenzene H.sub.2(BDC[CH.sub.3].sub.4)
H.sub.2O.sub.2 0.185 mmol MO25 Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O
DMF 90 112.0 90 23.880 16.834 18- .389 P2(1)/c 0.084 mmol BPhDC
0.085 mmol Cu-Thio Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O DEF 90
113.6 90 15.4747 14.51- 4 14.032 P2(1)/c 0.084 mmol
thiophenedicarboxylic acid 0.085 mmol CIBDC1
Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O 0.084 mmol DMF 90 105.6 90
14.911 15.622 18.413 C2/c H.sub.2(BDCCl.sub.2) 0.085 mmol MOF-101
Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O DMF 90 90 90 21.607 20.607 20-
.073 Fm3m 0.084 mmol BrBDC 0.085 mmol Zn.sub.3(BTC).sub.2
ZnCl.sub.2 DMF 90 90 90 26.572 26.572 26.572 Fm-3m 0.033 mmol EtOH
H.sub.3BTC base 0.033 mmol added MOF-j
Co(CH.sub.3CO.sub.2).sub.2.cndot.4H.sub.2O H.sub.2O 90 112.0 90
17.4- 82 12.963 6.559 C2 (1.65 mmol) H.sub.3(BZC) (0.95 mmol) MOF-n
Zn(NO.sub.3).sub.2.cndot.6H.sub.2O ethanol 90 90 120 16.711 16.711
1- 4.189 P6(3)/mcm H.sub.3(BTC) PbBDC Pb(NO.sub.3).sub.2 DMF 90
102.7 90 8.3639 17.991 9.9617 P2(1)/n (0.181 mmol) ethanol
H.sub.2(BDC) (0.181 mmol) Znhex Zn(NO.sub.3).sub.2.cndot.6H.sub.2O
DMF 90 90 120 37.1165 37.117 30.0- 19 P3(1)c (0.171 mmol) p-xylene
H.sub.3BTB ethanol (0.114 mmol) AS16 FeBr.sub.2 DMF 90 90.13 90
7.2595 8.7894 19.484 P2(1)c 0.927 mmol anhydr. H.sub.2(BDC) 0.927
mmol AS27-2 FeBr.sub.2 DMF 90 90 90 26.735 26.735 26.735 Fm3m 0.927
mmol anhydr. H.sub.3(BDC) 0.464 mmol AS32 FeCl.sub.3 DMF 90 90 120
12.535 12.535 18.479 P6(2)c 1.23 mmol anhydr. H.sub.2(BDC) ethanol
1.23 mmol AS54-3 FeBr.sub.2 DMF 90 109.98 90 12.019 15.286 14.399
C2 0.927 anhydr. BPDC n-
0.927 mmol propanol AS61-4 FeBr.sub.2 pyridine 90 90 120 13.017
13.017 14.896 P6(2)c 0.927 mmol anhydr. m-BDC 0.927 mmol AS68-7
FeBr.sub.2 DMF 90 90 90 18.3407 10.036 18.039 Pca2.sub.1 0.927 mmol
anhydr. m-BDC pyridine 1.204 mmol Zn(ADC)
Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DMF 90 99.85 90 16.764 9.349 9.-
635 C2/c 0.37 mmol chlorobenzene H.sub.2(ADC) 0.36 mmol MOF-12
Zn(NO.sub.3).sub.2.cndot.6H.sub.2O ethanol 90 90 90 15.745 16.907
1- 8.167 Pbca Zn.sub.2(ATC) 0.30 mmol H.sub.4(ATC) 0.15 mmol MOF-20
Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DMF 90 92.13 90 8.13 16.444
12.8- 07 P2(1)/c ZnNDC 0.37 mmol chlorobenzene H.sub.2NDC 0.36 mmol
MOF-37 Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DEF 72.38 83.16 84.33
9.952 11.5- 76 15.556 P-1 0.20 mmol chlorobenzene H.sub.2NDC 0.20
mmol Zn(NDC) Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DMSO 68.08 75.33
88.31 8.631 10- .207 13.114 P-1 (DMSO) H.sub.2NDC Zn(NDC)
Zn(NO.sub.3).sub.2.cndot.6H.sub.2O 90 99.2 90 19.289 17.628 15.05-
2 C2/c H.sub.2NDC Zn(HPDC) Zn(NO.sub.3).sub.2.cndot.4H.sub.2O DMF
107.9 105.06 94.4 8.326 12- .085 13.767 P-1 0.23 mmol H.sub.2O
H.sub.2(HPDC) 0.05 mmol Co(HPDC) Co(NO.sub.3).sub.2.cndot.6H.sub.2O
DMF 90 97.69 90 29.677 9.63 7.- 981 C2/c 0.21 mmol H.sub.2O/
H.sub.2(HPDC) ethanol 0.06 mmol Zn.sub.3(PDC)2.5
Zn(NO.sub.3).sub.2.cndot.4H.sub.2O DMF/ 79.34 80.8 85.83 - 8.564
14.046 26.428 P-1 0.17 mmol CIBz H.sub.2(HPDC) H.sub.20/ 0.05 mmol
TEA Cd.sub.2(TPDC)2 Cd(NO.sub.3).sub.2.cndot.4H.sub.2O methanol/
70.59 72.75 8- 7.14 10.102 14.412 14.964 P-1 0.06 mmol CHP
H.sub.2(HPDC) H.sub.2O 0.06 mmol Tb(PDC)1.5
Tb(NO.sub.3).sub.3.cndot.5H.sub.2O DMF 109.8 103.61 100.14 9.82- 9
12.11 14.628 P-1 0.21 mmol H.sub.2O/ H.sub.2(PDC) ethanol 0.034
mmol ZnDBP Zn(NO.sub.3).sub.2.cndot.6H.sub.2O MeOH 90 93.67 90
9.254 10.762 27.- 93 P2/n 0.05 mmol dibenzyl phosphate 0.10 mmol
Zn.sub.3(BPDC) ZnBr.sub.2 DMF 90 102.76 90 11.49 14.79 19.18 P21/n
0.021 mmol 4,4'BPDC 0.005 mmol CdBDC
Cd(NO.sub.3).sub.2.cndot.4H.sub.2O DMF 90 95.85 90 11.2 11.11 16.71
- P21/n 0.100 mmol Na.sub.2SiO.sub.3 H.sub.2(BDC) (aq) 0.401 mmol
Cd-mBDC Cd(NO.sub.3).sub.2.cndot.4H.sub.2O DMF 90 101.1 90 13.69
18.25 14.- 91 C2/c 0.009 mmol MeNH.sub.2 H.sub.2(mBDC) 0.018 mmol
Zn.sub.4OBNDC Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DEF 90 90 90 22.35
26.05 - 59.56 Fmmm 0.041 mmol MeNH.sub.2 BNDC H.sub.2O.sub.2
Eu(TCA) Eu(NO.sub.3).sub.3.cndot.6H.sub.2O DMF 90 90 90 23.325
23.325 23.3- 25 Pm-3n 0.14 mmol chlorobenzene TCA 0.026 mmol
Tb(TCA) Tb(NO.sub.3).sub.3.cndot.6H.sub.2O DMF 90 90 90 23.272
23.272 23.3- 72 Pm-3n 0.069 mmol chlorobenzene TCA 0.026 mmol
Formates Ce(NO.sub.3).sub.3.cndot.6H.sub.2O H.sub.2O 90 90 120
10.668 10.6- 67 4.107 R-3m 0.138 mmol ethanol formic acid 0.43 mmol
FeCl.sub.2.cndot.4H.sub.2O DMF 90 90 120 8.2692 8.2692 63.566 R-3c
5.03 mmol formic acid 86.90 mmol FeCl.sub.2.cndot.4H.sub.2O DEF 90
90 90 9.9364 18.374 18.374 Pbcn 5.03 mmol formic acid 86.90 mmol
FeCl.sub.2.cndot.4H.sub.2O DEF 90 90 90 8.335 8.335 13.34 P-31c
5.03 mmol formic acid 86.90 mmol NO330 FeCl.sub.2.cndot.4H.sub.2O
form- 90 90 90 8.7749 11.655 8.3297 Pnna 0.50 mmol amide formic
acid 8.69 mmol NO332 FeCl.sub.2.cndot.4H.sub.2O DIP 90 90 90
10.0313 18.808 18.355 Pbcn 0.50 mmol formic acid 8.69 mmol NO333
FeCl.sub.2.cndot.4H.sub.2O DBF 90 90 90 45.2754 23.861 12.441 Cmcm
0.50 mmol formic acid 8.69 mmol NO335 FeCl.sub.2.cndot.4H.sub.2O
CHF 90 91.372 90 11.5964 10.187 14.945 P2- 1/n 0.50 mmol formic
acid 8.69 mmol NO336 FeCl.sub.2.cndot.4H.sub.2O MFA 90 90 90
11.7945 48.843 8.4136 Pbcm 0.50 mmol formic acid 8.69 mmol NO13
Mn(Ac).sub.2.cndot.4H.sub.2O ethanol 90 90 90 18.66 11.762 9.418
Pbcn- 0.46 mmol benzoic acid 0.92 mmol bipyridine 0.46 mmol NO29
Mn(Ac).sub.2.cndot.4H.sub.2O DMF 120 90 90 14.16 33.521 33.521 P-1
MOF-0 0.46 mmol similar H.sub.3BTC 0.69 mmol Mn(hfac).sub.2
Mn(Ac).sub.2.cndot.4H.sub.2O ether 90 95.32 90 9.572 17.162- 14.041
C2/c (O.sub.2CC.sub.6H.sub.5) 0.46 mmol Hfac 0.92 mmol bipyridine
0.46 mmol BPR43G2 Zn(NO.sub.3).sub.2.cndot.6H.sub.2O DMF 90 91.37
90 17.96 6.38 7.19- C2/c 0.0288 mmol CH.sub.3CN H.sub.2BDC 0.0072
mmol BPR48A2 Zn(NO.sub.3).sub.26H.sub.2O DMSO 90 90 90 14.5 17.04
18.02 Pbca 0.012 mmol toluene H.sub.2BDC 0.012 mmol BPR49B1
Zn(NO.sub.3).sub.26H.sub.2O DMSO 90 91.172 90 33.181 9.824 17.884 -
C2/c 0.024 mmol methanol H.sub.2BDC 0.048 mmol BPR56E1
Zn(NO.sub.3).sub.26H.sub.2O DMSO 90 90.096 90 14.5873 14.153 17.18-
3 P2(1)/n 0.012 mmol n- H.sub.2BDC propanol 0.024 mmol BPR68D10
Zn(NO.sub.3).sub.26H.sub.2O DMSO 90 95.316 90 10.0627 10.17 16.41-
3 P2(1)/c 0.0016 mmol benzene H.sub.3BTC 0.0064 mmol BPR69B1
Cd(NO.sub.3).sub.24H.sub.2O DMSO 90 98.76 90 14.16 15.72 17.66 Cc
0.0212 mmol H.sub.2BDC 0.0428 mmol BPR73E4
Cd(NO.sub.3).sub.24H.sub.2O DMSO 90 92.324 90 8.7231 7.0568 18.438-
P2(1)/n 0.006 mmol toluene H.sub.2BDC 0.003 mmol BPR76D5
Zn(NO.sub.3).sub.26H.sub.2O DMSO 90 104.17 90 14.4191 6.2599 7.061-
1 Pc 0.0009 mmol H.sub.2BzPDC 0.0036 mmol BPR80B5
Cd(NO.sub.3).sub.2.cndot.4H.sub.2O DMF 90 115.11 90 28.049 9.184 1-
7.837 C2/c 0.018 mmol H.sub.2BDC 0.036 mmol BPR80H5
Cd(NO.sub.3).sub.24H.sub.2O DMF 90 119.06 90 11.4746 6.2151 17.268-
P2/c 0.027 mmol H.sub.2BDC 0.027 mmol BPR82C6
Cd(NO.sub.3).sub.24H.sub.2O DMF 90 90 90 9.7721 21.142 27.77 Fdd2
0.0068 mmol H.sub.2BDC 0.202 mmol BPR86C3
Co(NO.sub.3).sub.26H.sub.2O DMF 90 90 90 18.3449 10.031 17.983 Pca-
2(1) 0.0025 mmol H.sub.2BDC 0.075 mmol BPR86H6
Cd(NO.sub.3).sub.2.cndot.6H.sub.2O DMF 80.98 89.69 83.412 9.8752 1-
0.263 15.362 P-1 0.010 mmol H.sub.2BDC 0.010 mmol
Co(NO.sub.3).sub.26H.sub.2O NMP 106.3 107.63 107.2 7.5308 10.942
11.025 P- 1 BPR95A2 Zn(NO.sub.3).sub.26H.sub.2O NMP 90 102.9 90
7.4502 13.767 12.713 P- 2(1)/c 0.012 mmol H.sub.2BDC 0.012 mmol
CuC.sub.6F.sub.4O.sub.4 Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O DMF 90
98.834- 90 10.9675 24.43 22.553 P2(1)/n 0.370 mmol chloro
H.sub.2BDC(OH).sub.2 benzene 0.37 mmol Fe formic
FeCl.sub.2.cndot.4H.sub.2O DMF 90 91.543 90 11.495 9.963 14.48 P-
2(1)/n 0.370 mmol formic acid 0.37 mmol Mg formic
Mg(NO.sub.3).sub.2.cndot.6H.sub.2O DMF 90 91.359 90 11.383 9.932-
14.656 P2(1)/n 0.370 mmol formic acid 0.37 mmol
MgC.sub.6H.sub.4O.sub.6 Mg(NO.sub.3).sub.2.cndot.6H.sub.2O DMF 90
96.624 9- 0 17.245 9.943 9.273 C2/c 0.370 mmol H.sub.2BDC(OH).sub.2
0.37 mmol ZnC.sub.2H.sub.4BDC ZnCl.sub.2 DMF 90 94.714 90 7.3386
16.834 12.52 P2(1)/- n MOF-38 0.44 mmol CBBDC 0.261 mmol MOF-49
ZnCl.sub.2 DMF 90 93.459 90 13.509 11.984 27.039 P2/c 0.44 mmol
CH.sub.3CN m-BDC 0.261 mmol MOF-26
Cu(NO.sub.3).sub.2.cndot.5H.sub.2O DMF 90 95.607 90 20.8797 16.017
- 26.176 P2(1)/n 0.084 mmol DCPE
0.085 mmol MOF-112 Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O DMF 90
107.49 90 29.3241 21.2- 97 18.069 C2/c 0.084 mmol ethanol
o-Br-m-BDC 0.085 mmol MOF-109 Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O
DMF 90 111.98 90 23.8801 16.8- 34 18.389 P2(1)/c 0.084 mmol KDB
0.085 mmol MOF-111 Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O DMF 90
102.16 90 10.6767 18.7- 81 21.052 C2/c 0.084 mmol ethanol o-BrBDC
0.085 mmol MOF-110 Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O DMF 90 90
120 20.0652 20.065 - 20.747 R-3/m 0.084 mmol thiophenedicarboxylic
acid 0.085 mmol MOF-107 Cu(NO.sub.3).sub.2.cndot.2.5H.sub.2O DEF
104.8 97.075 95.206 11.03- 2 18.067 18.452 P-1 0.084 mmol
thiophenedicarboxylic acid 0.085 mmol MOF-108 Cu(NO3)2.cndot.2.5H2O
DBF/ 90 113.63 90 15.4747 14.514 14.032 C2/c- 0.084 mmol methanol
thiophenedicarboxylic acid 0.085 mmol MOF-102 Cu(NO3)2.cndot.2.5H2O
DMF 91.63 106.24 112.01 9.3845 10.794 10.831- P-1 0.084 mmol
H2(BDCCl2) 0.085 mmol Clbdc1 Cu(NO3)2.cndot.2.5H2O DEF 90 105.56 90
14.911 15.622 18.413 P-1 0.084 mmol H2(BDCCl2) 0.085 mmol Cu(NMOP)
Cu(NO3)2.cndot.2.5H2O DMF 90 102.37 90 14.9238 18.727 15.529 P2(1-
)/m 0.084 mmol NBDC 0.085 mmol Tb(BTC) Tb(NO3)3.cndot.5H2O DMF 90
106.02 90 18.6986 11.368 19.721 0.033 mmol H3BTC 0.033 mmol
Zn3(BTC)2 ZnCl2 DMF 90 90 90 26.572 26.572 26.572 Fm-3m Honk 0.033
mmol ethanol H3BTC 0.033 mmol Zn4O(NDC) Zn(NO3)2.cndot.4H2O DMF 90
90 90 41.5594 18.818 17.574 aba2 0.066 mmol ethanol 14NDC 0.066
mmol CdTDC Cd(NO3)2.cndot.4H2O DMF 90 90 90 12.173 10.485 7.33 Pmma
0.014 mmol H2O thiophene 0.040 mmol DABCO 0.020 mmol IRMOF-2
Zn(NO3)2.cndot.4H2O DEF 90 90 90 25.772 25.772 25.772 Fm-3m 0.160
mmol o-Br-BDC 0.60 mmol IRMOF-3 Zn(NO3)2.cndot.4H2O DEF 90 90 90
25.747 25.747 25.747 Fm-3m 0.20 mmol ethanol H2N-BDC 0.60 mmol
IRMOF-4 Zn(NO3)2.cndot.4H2O DEF 90 90 90 25.849 25.849 25.849 Fm-3m
0.11 mmol [C3H7O]2-BDC 0.48 mmol IRMOF-5 Zn(NO3)2.cndot.4H2O DEF 90
90 90 12.882 12.882 12.882 Pm-3m 0.13 mmol [C5H11O]2-BDC 0.50 mmol
IRMOF-6 Zn(NO3)2.cndot.4H2O DEF 90 90 90 25.842 25.842 25.842 Fm-3m
0.20 mmol [C2H4]-BDC 0.60 mmol IRMOF-7 Zn(NO3)2.cndot.4H2O DEF 90
90 90 12.914 12.914 12.914 Pm-3m 0.07 mmol 1,4NDC 0.20 mmol IRMOF-8
Zn(NO3)2.cndot.4H2O DEF 90 90 90 30.092 30.092 30.092 Fm-3m 0.55
mmol 2,6NDC 0.42 mmol IRMOF-9 Zn(NO3)2.cndot.4H2O DEF 90 90 90
17.147 23.322 25.255 Pnnm 0.05 mmol BPDC 0.42 mmol IRMOF-10
Zn(NO3)2.cndot.4H2O DEF 90 90 90 34.281 34.281 34.281 Fm-3m 0.02
mmol BPDC 0.012 mmol IRMOF-11 Zn(NO3)2.cndot.4H2O DEF 90 90 90
24.822 24.822 56.734 R-3m 0.05 mmol HPDC 0.20 mmol IRMOF-12
Zn(NO3)2.cndot.4H2O DEF 90 90 90 34.281 34.281 34.281 Fm-3m 0.017
mmol HPDC 0.12 mmol IRMOF-13 Zn(NO.sub.3).sub.2.cndot.4H.sub.2O DEF
90 90 90 24.822 24.822 56.- 734 R-3m 0.048 mmol PDC 0.31 mmol
IRMOF-14 Zn(NO.sub.3).sub.2.cndot.4H.sub.2O DEF 90 90 90 34.381
34.381 34.- 381 Fm-3m 0.17 mmol PDC 0.12 mmol IRMOF-15
Zn(NO.sub.3).sub.2.cndot.4H.sub.2O DEF 90 90 90 21.459 21.459 21.-
459 Im-3m 0.063 mmol TPDC 0.025 mmol IRMOF-16
Zn(NO.sub.3).sub.2.cndot.4H.sub.2O DEF 90 90 90 21.49 21.49 21.49-
Pm-3m 0.0126 mmol NMP TPDC 0.05 mmol ADC Acetylenedicarboxylic acid
NDC Naphthalenedicarboxylic acid BDC Benzenedicarboxylic acid ATC
Adamantanetetracarboxylic acid BTC Benzenetricarboxylic acid BTB
Benzenetribenzoic acid MTB Methanetetrabenzoic acid ATB
Adamantanetetrabenzoic acid ADB Adamantanedibenzoic acid
Further metal-organic frameworks are MOF-2 to 4, MOF-9, MOF-31 to
36, MOF-39, MOF-69 to 80, MOF103 to 106, MOF-122, MOF-125, MOF-150,
MOF-177, MOF-178, MOF-235, MOF-236, MOF-500, MOF-501, MOF-502,
MOF-505, IRMOF-1, IRMOF-61, IRMOP-13, IRMOP-51, MIL-17, MIL-45,
MIL-47, MIL-53, MIL-59, MIL-60, MIL-61, MIL-63, MIL-68, MIL-79,
MIL-80, MIL-83, MIL-85, CPL-1 to 2, SZL-1, which are described in
the literature.
Particularly preferred metal-organic frameworks are MIL-53,
Zn-tBu-isophthalic acid, Al-BDC, MOF-5, MOF-177, MOF-505, IRMOF-8,
IRMOF-11, Cu-BTC, Al-NDC, Al-aminoBDC, Cu-BDC-TEDA, Zn-BDC-TEDA,
Al-BTC, Cu-BTC, Al-NDC, Mg-NDC, Al-fumarate,
Zn-2-methylimidazolate, Zn-2-aminoimidazolate,
Cu-biphenyldicarboxylate-TEDA, MOF-74, Cu-BPP, Sc-terephthalate.
Greater preference is given to Sc-terephthalate, Cu-BTC, Al-BDC and
Al-BTC. However, owing to their environmental compatibility, very
particular preference is given to Mg-formate, Mg-acetate and
mixtures thereof.
Apart from the conventional method of preparing the MOFs, as
described, for example, in U.S. Pat. No. 5,648,508, these can also
be prepared by an electrochemical route. In this respect, reference
is made to DE-A 103 55 087 and WO-A 2005/049892. The metal-organic
frameworks prepared in this way have particularly good properties
with regard to the adsorption and desorption of chemical
substances, in particular gases.
Regardless of the method of preparation, the metal-organic
framework is generally obtained in pulverulent or crystalline form.
This can be used as sorbent as such either alone or together with
other sorbents or further materials. The metal-organic framework
can also be converted into a shaped body.
Preference is also given to the at least one metal-organic
framework being present in a proportion of from 0.01% by weight to
10% by weight based on the total weight of the polymer. More
preferred is from 0.1 wt.-% to 10 wt.-%, more preferred 1 wt.-% to
10 wt.-%, more preferred 1 wt.-% to 5 wt.-%.
The present invention further provides food packaging comprising a
biodegradable material according to the invention. The food
packaging is preferably fruit or vegetable packaging.
The present invention further provides for the use of a material
according to the invention for the packaging of foods.
The present invention further provides for the use of a porous
metal-organic framework for the absorption of ethene in food
packaging.
EXAMPLES
Example 1
Preparation of a Magnesium Formate-Based Metal-Organic
Framework
TABLE-US-00002 1) Magnesium nitrate * 6 water 38.5 mmol 9.90 g 2)
Formic acid 106.5 mmol 4.8 g 3) DMF 2.19 mol 160.0 g
The magnesium nitrate is dissolved in DMF in an autoclave liner.
The formic acid is added and the solution is stirred for 10
minutes. (pH-3.49)
Crystallization:
125.degree. C./78 h
Removal from autoclave:
Clear solution with white crystals
Work-Up:
The crystals are filtered off and washed twice with 50 ml of
DMF.
Weight obtained: 5.162 g
Example 2
Production of a Biodegradable Foil Comprising a Metal-Organic
Framework Using Laboratory Equipment
10 g of Ecoflex.RTM. pellets are dissolved in CHCl.sub.3 or
CH.sub.2Cl.sub.2 to obtain a solution comprising 10% by weight of
polymer. This solution is stirred overnight at room temperature. 1%
by weight (example 2a) or 5% by weight (example 2b) of framework
from example 1 are then added. The suspension obtained is stirred
for about 30 minutes until homogeneous. The suspension is spread on
a glass plate by means of a doctor blade. Evaporation of the
solvent gives, after about 1 hour, a film on the glass plate, which
can be detached from the plate, if appropriate with the aid of a
little water, to give a foil.
Example 3
Adsorption Measurement
An adsorption/desorption measurement is carried out on the
framework from example 1 using a Rubotherm magnetic suspension
balance (metal version with metering system).
FIG. 1 shows the ethene absorption at 298 K. Here, the absorption A
(in mg of ethene/g of framework) is shown as a function of the
absolute pressure P (in mbar).
Example 4
Influence of Framework on the Ripening Process of a Fruit
About 600 g of bananas are stored in a dry vessel at room
temperature for 12 days together with 1 g of framework from example
1 (4a) and without framework (4b).
The bananas then have the following nature:
TABLE-US-00003 With MOF (4a) Without MOF (4b) Consistency Soft very
soft to mushy Odor Sweetish rotten
It can be seen than the ripening process of the bananas is reduced
by the presence of the metal-organic framework.
Example 5
Gas Adsorption Properties for Ethylene
The following table shows the uptake capacity for ethylene of
various sorption materials at room temperature and 1 bar.
TABLE-US-00004 Langmuir surface area ethylene uptake material
(m.sup.2/g) (wt.-%) Active carbon 1900 -- Zeolite 13X 700 8
Mg-Formte MOF (Exa. 1) 500-600 8 Cu-BTC MOF (Basolite .RTM. C 1200
17 300)
Example 6
Ethylene Permeability of an Ecoflex.RTM. Film
The framework material of example 1 is used as additive in a
biologically de-gradable film with branch name Ecoflex.RTM. and the
permeability is determined. The following table shows the data
obtained.
TABLE-US-00005 Film thickness Permeability wt.-% MOF (.mu.m)
(cm.sup.3 * 1 .mu.m/m.sup.3/d/bar) 0 223.3 5.00E+04 0 191.8
5.16E+04 1 199.8 5.59E+04 1 207.3 1.01E+05 1 196.4 1.18E+05 1 172.8
1.23E+05 5 198.1 5.63E+04 5 225.2 1.14E+05 5 194.4 1.20E+05 5 206.4
1.13E+05
* * * * *